Organic nitrogenous base derivatives of ether derivatives and method of making same



Patented Sept-9; 194

- oaoamc lm'noeauoue use amnrwas or 1mm nmva'nvnsann turnover-mom BcniaminB. Harrh,Ghleagc,llL' N Drawing. orlglnnl' 0m rote-u, u,

, 1938.8erlnlN1a1NJl5- Dlvidodandthisapnuml nmy1, 1 m.8erium.m.1u

* ncmnn. 101.204)? M invention relates to nevvchemical compounds exam ternm ammonium type whi h are oharacterize l i by interface modify- (4) -BI- r-93 -Q! N IB: ing properties rendering th same highly usei'ui' 8 it our. iorthcpurposesiorwhiohsuchagenteareemo- I v. nloyed in thevarious arts. The invention also 0) 4 c1340! w'tlln lniiermedlafu 88 Well. 88 method! c1nn-c--o--on;-'on,--o-onr-on,-N oim" oi preparing the compounds. n q I o H -Thenovelcompounds,ingeneral,i'allwithin the scope or the general iormula v 10 a .Ro ucxY) a (my) cnmrc o-onron-oni-mon l-on-om g I b i 1; wherein' R is a higher molecular weig ht organic dim. x and Y are hydrogen, in. mm r 15 (heHa-G-O-QIJBFCHo-O One-Clio -O Ha other anions such as halocen, sulphon'lc, sulphate, g l on. phosphate, borate, or the like, A is an anion, prcierably of a solubilizing character, n and t are g c ,3 o-cn em 0 cn,-cn,-N j whole numbers, preferably 2; 8 or 4, m is a-whoie I 1 number.prei'erably 1, 2.30:4 although it maybe 8 t much higher, and at least one 6i the three indicated valence bonds attached to nitrogen is satisitr R I fled by a radical or the class 'oohsistlngof alkyls. o Y o1 cycloalkyls, alkylols, -aralkyls, ary1s,'aralkylols a and the radical of a heterocyclic ring or which -2 CnBn-C-OCHr-CBr-Q-OHr-CHz-l6 the nitrogen is'a member. i a

A more limited aspect or my invention may be represented by the general formula (u) n-c-o-cm-cm-o-cm-cn N CBI-(CHflo-CH-O-O-OHrCBs-O-QHa-Cflr v I v p v E wherein R is a hydrocarbon radical or substituted hydrocarbon radical containing at 'least nve and a v I preferably from eleven to seventeen carbon atoms. (12) 0.x;

The radical R in the above 1011111118 maybe 01 35 c. o. cn, -c o cg,.- qg, ng m aliphatic, cycloaliphatic, aromatic or aromaticaliphatic character, as will-be pointed out n i- 'inaiter, but it is preferred that it be aliphatic and or higher molecular weight. 4 I v In order that the nature or the invention may (m v become apparent, I list hereinbelow representa- 1 tiveeompounds' which fall within the scope ct my O --9 0 bf invention. I 4 A? tom (1) cnnri-o-om-om-o-om cnPg- M p 1- 16) Br CH:

vessel.-, The solution darkened considerably as soon'as all of the soap had dissolved. When the reaction was completed,' the solution was decanted from the sodium chloride precipitate and 'the excess dichlor ethyl ether was removed by distillation in vacuo at 150-170 degrees C. The resulting product was'a clear brown liquid.

rCIHr OH: I

l l 1 l (28) CuHafCf-O-CHrCHrO-CHg-CHg-O-CHy-CHKI (2 CnHu-O-OBramcm-cm-o-cm-cnEo-cm-cma:

The following examples are illustrative of methods which I have found suitable for preparing various of the compounds which I disclose herein.

It will be appreciated that other methods may be utilized, that the proportions of re acting-ingredients, times of reaction, and temperatures may be varied and that supplementaryprocesses of purification and the like may be resorted to wherever found desirable or convenient. These and other variations and modifications will be evident to those skilledin the art in the light of the guiding principles which I disclose herein.

, Example A Mixed cocoanut oil fatty acid mono ester of diethylene glycol pyridinium. chloride.

(A) 100'parts by weight of cocoanut oil mixed fatty acids were dissolved in 200 parts by weight or ethyl'alcohol and the, solution was then neutralized to phenolphthalein' with alcoholic potash. The alcohol was then removed by evaporating on a boiling water bath and the resulting 75 (C) 25 parts by weight of said clear brown liquid as produced in part (B) were dissolved in 25 parts by weight of pyridine and heated on an oil bath for about 5 hours at 170 degrees C. until the material in the reaction vessel became viscous. It was then heated for an additional 3 hours after which the excess pyridine was removed by distillation in vacuo at degrees C.

A dark product was obtained, at least th pre- 4 dominant portion of which-corresponded to the following formula:

wherein RCO corresponds to the acyl radicals found in cocoanut -oil mixed fatty acids.

' Example B Mono oleic acid ester of diethyl'ene glycol pyridinium chloride.

(A) 20 parts by weight of dried sodium oleate were refluxed with IOO-parts'by weight of sym- 1 J f 3! 3 meh'ical-dichlor ethyl etherattheboilingpoint 0 of the mixture forabout 4 hours. when the rem 3' f action was completed. the solution was decanted F Mill-01MB froan mtlzesodiummchllloride gyhiclzh had precipitated oom-om-ci an; excess 0 ore le erwasremovedii by distiliiation in vacuo at 160-170 degrees c. m m

'(B) The resulting product was then reacted 3 with an equal lagount of pyridine as described in nit-o-cm-esr-cl Example A; v illmlin'oduc consistedpredom- (o m'o-o-hn emm ofacompound having the following i'o r-v H v HPOH'OB Grilla-OHEs-CHPO-OFPCHPf 5 I a v l v 334mm c nd-o-cm-omon Mono stearic acid ester of dlethylene glycol pyridiniumohloride.

. This product was made in the same way as described hereinabove in Example B, employing the same proportions of reactants, using sodium stearate in place of sodium 0 eater Instead of preparing the oaps as described in part A of Example A, an alternative procedure ha proved highly satisfactory. In accordance with this latter procedure, hlgher fatty acids,

such as lauric acid or cocoanut oil mixed fatty acids, are melted and introduced into-a hot aque- It is. of course, clear that'methods other than those described may be employed for producing the novel compounds of my invention. Thus, for example, chlorhydrins or halogenhydrins of diethylene glycol (CHIHa-CHr-O-CHa-CHzOH) and similar halogen derivatives of polyslycols, -polyglycerols and the like may initially be reacted with higher fatty acids or the like to produce esters in accordance with the 'following reaction:

ous solutionof alkali such as potassium hydroxide or sodium hydroxide, the mass being stirred until combination ofthefatty acids with'the alkali has taken place to form soap. The alkali should preferably be used in stoichiometric amounts to form the soap. To the hot, aqueous soap solution, common salt is added until the soap separates out, the salt solution then beingseparated from the soap. The soap solidifies at room temperature to a crumbly mass which loses itswater easily-by drying in air. Tofacilitate the yin the air may be heated slightly. This soap product may then be reacted with dichlorethyl' ether and then with pyridine, as described in parts Band 0 of Example A. The final product, when prepared from lauric acid soap or soaps of cocoanut oil mixed fatty acids,-as Just described, possesses useful properties in are flotation operations, particularly for separating quartz and "feldspar. In this connection, tbsp of the flotation circuit should preferably be-between 7 and 9, under which conditions the silica floats ahead of the feldspar and good separations can be made by controlling the amount of the reagent. t

It will be understood, particularly in the light of the examples hereinabove, that my novel compounds may contain one or more ether linkages. Thus, for example, in placeof employing symmetrical dichlorethyl ether orthe chlorhydrin of diethylene glycol having a plurality of ether linkages such as the following, by way of illustration:

R-O-O-CHr-OHg-O-CHr-CHCI The resulting product may then be reacted with an organic nitrogenous base such as pyridine to produce the compounds of my'inve'ntion. Still other methods will suggest themselves to those versed in the art in the light of my teachings herein.

At this time, it may also be pointed. out that all of the products of my invention possess utility in ore flotation and ore separation processes.

-' They appear to function as cationic reagents and,

As Examples 8, l7 and 18 show, my. compounds may also. comprise higher molecular weight ether derivatives. The higher molecular weight ethers may be prepared, for example, by

Kc) HO-OHr-CHr-O-CHs-OIk-O-CHa-GB's-Cl o HO-CHs-CHrO-CHs-CHs-O-OB's-CBs-OCHrCHs-Cl reacting acompound containing a reactive halogen, f or-example, dichlor ethyl ether with an alkali metal alcoholate such as sodium laurylate (came-0m) in accordance with general methods known in the art. The resulting compound may then be treated with pyridine or other desired nitrogenous to produce compounds in accordance with 'my invention. In-

general, I find that the higher molecular weight, esters are more satisfactory for most purposes.

The higher molecular weight organic radical.

represented by R. in the general formulae may, as

stated, be derived from various sources.- Among such sources may be mentioned straight chain and branched chain higher molecular weight car-'- bonlic, aliphatic, and fatty acids, saturated and unsaturated, such as caprylic acid, caproic acid,

capric acid, sebacic acid, behenic acid, arachidic ,acid, cerotic acid, erucic' acid, melissic acid, stearic acid,o1elc acid," ricinoleic acid,-iinoleic acid, linolenic acid, lauric acid, myristic acid.

palmitic acid, mixtures of any two or more of the above mentioned acids or other acids, mixed higher fatty acids derived from animal or vege- I hydroxy stearic acid, alpha-hydroxy palmitic acid,

alpha-hydroxy lauric acid, alpha-hydroxy coconut oil mixed fatty acids, and the like; fatty acids derived from various waxes such as beeswax, spermaceti, montan wax, and earnauba wax and carboxylic acids derived, by oxidatlonand other methods, from petroleum; cycloaliphatic and hydroaromatic acids such as hexahydrobenzoic acid, resinic acids, naphthenic acid and abietic acid; aromatic acids such as phthalic acid, benzoic acid, naphthoic acid, pyridine carboxylic acids; hydroxy aromatic acids such as salicyclic acid, hydroxy benzoic and naphthoic aids, and. the like; and substitution and addiion derivatives, particularly halogen substitution and addition derivatives of the aforementioned :arboxylic substances. It will be understood that mixtures of any two or more of said acids may be employed if desired.

In those cases where the higher molecular weight organic radical is derived from alcohols, such alcohols include those corresponding to the higher molecular weight acids referred to hereinabove as well as others as, for example, aliphatic straight chain and branched chain alcohols such as hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, oleyl alcohol, linoleyl alcohol, stearyl alcohol, ricinoleyl alcohol, palmitoleyl alcohol, melissyl alcohol, ceryl alcohol, carnaubyl alcohol, myricyl alcohol, branched chain octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl aliphatic alcohols as, for example, 2-ethyl hexanol-l, 2-n butyl octanol-l, 2-butyl tetradecanol-l, and, in general, the higher molecular weight saturated and unsaturated aliphatic straight chain and branched chain alcohols, preferably those corresponding to the fatty acids occurring in triglyceride oils and fats of vegetable or animal origin, natural or hydrogenated, such as corn oil, cottonseed oil, sesame oil, coconut oil, palm kernel oil, sunflower seed oil, lard, tallow, soya bean oil and the like, those alcohols containing from 12 to 18 carbon atoms being preferred. Other alcohols from which the radical R may be derived are cyclo-aliphatic or all-cyclic alcohols such as.

the sterols, as, for example, cholesterol, isocholesterol, phytosterol, sitosterol, hydro-aromatic alcohols such as abietol, and such unsaturated alcohols as linalool, citronellol, geraniol and the like. Also included within the class of alcohols which may be employed are such compounds as the hydroxy and alpha-hydroxy higher aliphatic and fatty acids as, for example, ricinoieic acid, alpha-hydroxy stearic acid, alphahydroxy lauric acid, di-hydroxy stearic acid, i-hydroxystearic acid, alpha-hydroxy palmitic acid, and the like, as well as esters of hydroxyfatty acids, suchas ethyl ricinoleate, castor oil, butyl alpha-hydroxy-stearate, cetyl hydroxystearate, and the like.

The term alcohols," as employed herein, is

intended to include alcohols which may or may not contain other groups such as carboxylic, halogen, sulphonic, sulphate, or other radicals. The alcohols obtainable by substituting alkyl or acyl radicals, preferably of high molecular weight, in place of the hydrogen of one or more hydroxy groups of polyhydroxy substances or polyhydric alcohols, it being understood that at least one hydroxy group attached to the nucleus of the polyhydroxy substance or polyhydric alcohol re- -mains, are also within the scope of the alcohols which may serve as source materials for the radical R of my compounds. As examples of such alcohols may be mentioned, partially esterifled or partially etherified sugars and sugar alcohols such as monolauric acid ester of sucrose, monostearicacid ester of dextrose, monopalmitic acid ester of mannitol, dicaproic acid ester of maltose, mono-octyl ether of sorbitol, monolauryl ether of pentaerythritol, monolauric acid ester of pentaerythritol, and the like; the monoglycerides and diglycerides, preferably of the higher fatty acids, as, for example, monolaurin, mono- .myristin, monostearin, distearin, diolein, dicaproin, mono.-lauryl ether of glycerol, dicetyl ether of glycerol, monostearic acid ester of diethylene glycol, monolauric acid ester of ethylene glycol, and the like. j

It is, of course, obvious that the alcohols may be prepared in accordance with any desired method. For exam'ple,many of these alcohols may be prepared by the so-called Bouveault and Blanc method or, alternatively, by the reduction or catalytic reduction with hydrogen of natural or hydrogenated animal or vegetable fats and oils in accordance with well known practices. Again the alcohols may be derived from synthetic processes suchas by the oxidation of hydrocarbons or may be prepared by 'saponification of waxes and the like. Alternatively, they'may be prepared by reduction of aldehydes or by the Grignard reaction.

It is likewise apparent that mixtures of the foregoing or other alcohols may be utilized as, for example, the mixture of alcohols resulting from the hydrogenation of coconut oil or the free fatty acids of coconut oil. Lauryl alcohol comprises about 45% of the total alcohol mixture, the remaining alcohols running from C6 to Cm.

Again; mixtures of alcohols such as are present in the so-called sperm oil alcohols, as well as those present in wool-fat, may equally efllcaciously be utilized. Indeed, these higher molecular weight alcohols are generally offered on the market in the form of mixtures of different alcohols. These alcohols maybe utilized, as previously indicated, in theform of alkali metal alcoholates for introducing ahigher molecular weight alkyl 'or similar radical into the molecule to produce'compounds falling within the scope of my invention;

It will be understood that, where the higher molecular weight esters are produced in accordance with the method described in the foregoing examples wherein my novel substances are prepared from halogen-containing compounds, the

higher organic or fatty acids or the like are employed in the form of salts or soaps thereof. As in the case of the use of the alcohols and as previously indicated, mixtures of higher organic or fatty acids maybe employed and, indeed, in commercial practice, it is found more convenient to do so than to attempt to obtain higher molecular weight acid fractions which consist primarily of only a single acid. a a

order to bring about softening and other skins. Their utility as emulsifying.agents en As a general rule, Lflndlthe halogen derivatives to be particularly satisfactory.

' The pentavalent nitrogen present in my new substances may be introduced into the molecule by meansof various organic nitrogenous bases as, for example, alcohol amines and a1kylol-, aryloland aralkyl ol amines includingmono diand triethanolamine and mixtures thereof such as are, for example, present in so-called commercial triet-hanolamine, propanolamines, butanolamines, pentanolamines, hexanolamines, glycerolamines, 'dibutyl ethanolamine, diethanol ethyl amine, cyclohexyl-ethanolamine, diethanol cyclohexylamine, ethanol aniline, alkylol poly-.

amines such as alkylol derivatives of ethylene di a min e, mono-methyl mono-ethanolamine, diethyi-monoethanolamine, 1-amino-2, 3 propanediol, 1,2-diaminopropanol; alkylamines such art in the light of my as butyl amine, hexylamine, dimethylamine,-'.

ethylene diamine, diethylene triamine, triethylene tetra-amine, mono-methyl ethylene diamine, mono-ethyl diethylene tetra-amine, mono-ally] amine, aromatic and heterocyclic bases such as benzylamine, cyclo-hexylethylaniline, morphoiine, pyridine, alkyl pyridines such as methyl-pyridine, piperidine, pyrrolidines, quinaldine, nicotine, and homologues and derivatives or substitution products thereof; mixtures of any two or more thereof, and the like. It will be understood, that these organic bases, as in the case of triethanolamine, for example, may be employed-in pure, impure, or commercial form.

The compounds of my for example, they and related induse ting, detergent, emulsifying, penetrating, dispersing, frothing and foaming purposes. The textiles, the treatment of which with the agents of thepresent invention is rendered effective, comprise natural products such as cotton, .wool, linen and the like as well as the artificially pro,- duced'fabrics such as rayon, cellulose acetates, cellulose ethers'and similar artificial silk fabrics. It will be understood, of course, that the agents may-be used in aqueous aloneor in combination with other suitable salts 5: organic or inorganic character or with other interface modifying agents. In the dyeingof textiles they may be employed asassistants in even level shades. They may be used in the leather industry as wetting agents in soaking,

treating baths for hides and ables them to be employed for the preparation of emulsions which may be used for insecticidal, fungicidal andfor similar agriculture They have utility in the preparation of cosmetic creams such as cold creams, vanishing creams, tissue creams, shaving creams of the brushless and lathering type and similar cosmetic preparations.. Another use to which theagents of my invention may be placed is for the treatment of invention have utility in various arts in which interface modifying agents are employed. 'Thus, .may be utilized in the textile and other media either,

dyeing, tanning and the genous base ls pyridine.

paper where they maybe employed, for example, 76

group hydrogen,

with the organic acid is first permitted to proceed after which the resulting compound isreacted with moniumv chemical industry wherein they function effectively in I froth flotation processes, particularly for the separation of silica from ores containing the same. ,Theirinterface modifying pr also permit their use in'lubricating oils and the like of effective boring Oils,

enabling theiproduction 7 cutting oils, drilling oils, wiredrawing oils, ex treme pressure lubricants and the like. They may lilsobe used with eifect in the preparation of metal and furniture polishes, shoe polishes. in rubber compositions, for breaking or demulsiryins Petroleum emulsions such as those of the water-in-oil type which are encountered in oilfield operations, and for various other purposes which will readily occur to those versed in thedisolosure herein.

Wherever the term "higher" is employed as referring to higher molecular weight organic acids, it will be understood to cover at least six carbon atoms unless otherwise specifically stated.

This application is adivislon of my earlier application Serial No. 190,135, filed February 11, 1938, Patent 2,189,397.

What I claim as new and desire Letters Patent of the United States 1. The process of monium chemic formula t protect by producing quaternary amal compounds having the general RO-KCXYh-OL-(CXYh-N wherein R is a higher molecular weight acyl radical; x is hydrogen, Y is a member of the hydroxy and inert anions, A is an anion, n. m and t are whole numbers and each of the three indicated valence bonds attached to nitrogen are linked directly to carbon which comprises the steps of reacting a salt of Y a higher molecular weight organic acid, a tertiary organic nitrogenous base, and a compound of the general formula halogen-[(CJIYh-Oh-(CXYh-halogen wherein x, Y and n, m and t have the foregoing significance.

2. The process of claim 1 wherein the reaction salt of the higher molecular weight th; t gltiary organic nitrogenous base. the higher molecular weight organic acid is a fatty acid soap and the tertiary organic nitroproducing quaternar amccmpoungs having the gen- 4. The. process of wherein v is a higher molecular weight acyl radical, A is an anion, and each ofthe three indicated valence bonds attached to nitrogen are linked directly e process of claim 1 wherein the salt ofv to carbon, which comprises the steps of reacting a salt of a higher molecular weight organic acid, a tertiary organic nitrogenous base, and a, compound or the generaliormula halogen-CHMHr-O-Cfi-Clh-halogen 5 5. The process of producing the compound wherein 15 is a higher molecular weight acyl radical which comprises reacting symmetrical dichlordiethylether with a salt of a higher molecular weight aliphatic acid, and then reacting the resulting 1 product with pyridine. 20 6. The process or claim 5 wherein the salt of the higher molecular weight aliphatic acid comprises a soap produced from higher fatty acids corresponding to those found-in waxes and triglyceride oils and fats.

. 5 7. Quaternary ammonium compounds corre- 2 spondin to the formula ao-uc-xr) .-o]..-(cxY wherein a is a higher molecular weight aliphatic radical, X is hydrogen. Y is. a member or the group'hydrogen, hydroxy and inert anions,-.A is

'an anion, n. m and t are whole numbers, and

each of the three indicated valence bonds at- 35 tached to nitrogen are linked directly to carbon.

8. Quaternary ammonium chemical compounds corresponding to the formula 0 wherein R is a higher molecular weight allryl radical, A is ananion, n is a whole number, and each of the three indicated valence bonds at-- tached to nitrogen are linked directly to carbon. 10. Chemical compounds in accordance with claim '7 wherein R is a fatty acid acyl radical containing from 12 to'18 carbons atoms and A is a halogen.

11. Chemical compounds in accordance with the formula wherein R is a' radical selected from the group consisting of higher molecular weight acyl and alkyl radicals, m is a whole number, and A is an anion.

BENJAMIN R. HARRIS. 

